DE1572256C3 - Photographic light-sensitive material containing an oxonol methine dye - Google Patents

Description

R'-C-

C-O P

Il /

-C-L '= (L ² -L ³ =) "C

(D

where mean:

R ^{1 is} an alkyl or aralkyl group,

L ¹ , L ² , L ³ each represent an identical or different methine group, which may be alkyl- or aralkyl-substituted,

η O or 1,

M® is a cation and

P and Q individually each represent a cyano group, a group of the formula —COOR ² , in which R ² denotes a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or a group of the formula -COR ³ in which R ³ denotes a methyl group. , Ethyl or phenyl group, or together those for closure

ίο one

Pyrazolone, isoxazolone, oxindole,
2,4,6-triketohexahydropyrimidine,
Rhodanine, 2-imidazo [l, 2-a] pyridone,
5,7-dioxo-6,7-dihydro-5H-thi-

azolo [3,2-a] pyrimidine-,

2-thio-2,4-oxazolidinedione,
Thianaphthenone,
2-thio-2,5-thiazolidinedione,
2,4-thiazolidinedione,

2-imino-4-thiazolidone, 4-thiazolone,

2-imino-4-oxazolidone,
2,4-imidazoIidinedione,
2-thio-2,4-imidazolidinedione or
5-imidazolone ring

required atoms.

2. Recording material according to claim 1, characterized in that the oxonol methine dye a compound of the general formula II is present:

N
R ¹ —C-

C-O

O = C

-C - L ⁴ = (L ⁵ - L ^ft =) "C-

Il

-CR ¹

M "

where mean:

R ^{1 is} an alkyl or aralkyl group,

L ⁴ , L ⁵ , L ⁶ each have an unsubstituted methine group,

Μ®

Oor 1 and
a cation.

3. Recording material according to claim 1 and 2, characterized in that the oxonol methine dye is in a silver halide emulsion layer.

The invention relates to a light-sensitive photographic recording material in at least one of its colloid layer (s) contains an oxonol methine dye.

From DE-AS 10 75 944 it is already known, in silver halide layers of light-sensitive photographic Recording materials to use methine dyes of the oxonol type. One in this The oxonol methine dye that is particularly recommended in an interpretation is bis - [(l-p-sulfophenyl) -3-methyl-5-pyrazolone-4] trimethine oxonol (hereinafter referred to as "dye B").

However, it has been found that these known oxonol methine dyes are relatively low Have coloring power and therefore in relatively large amounts in the photographic light-sensitive material must be incorporated so that the colloid layer (s) in which such a dye should be incorporated, cannot fall below a certain minimum thickness, which in particular in the case of multi-layer materials is significant, as this increases the possibilities of manufacturing today The thinnest possible photographic recording materials aimed for are limited (cf. results of comparative tests explained below). The object of the invention is therefore to provide a light-sensitive indicate photographic recording material in at least one of its colloid layers contains an oxonol methine dye having an increased tinting power, so that the colloid layers containing it and thus the entire photographic recording material can be kept as thin as possible. . It has now been found that this object can be achieved in a light-sensitive photographic recording medium.

material of the type mentioned can be solved in that as an oxonol methine dye Compound of general formula I is present:

Rl Γ * (° T 1— Π 2_ΐ 3_ \ / ~ ι

M® (I)

where mean:
Ri

ίο

15th

an alkyl or aralkyl group, ζ. B. a ■ methyl or benzyl group,
L ¹ , L ² , L ³ each represent an identical or different methine group, which may be alkyl- or aralkyl-substituted,

η Oor 1,

M ^, a cation, e.g. B. a proton, a metal cation

or an onium cation of the inorganic or organic type, e.g. B. an ammonium or pyridinium cation, and P and Q by themselves are each a cyano group, a group of the formula -COOR ² in which R ^{2 is} a hydrogen atom or an alkyl group with up to 4 carbon atoms, or a group of the formula -COR ³ , in which R ^{3 is} a methyl, ethyl or phenyl group, or together those for closure

a pyrazolone ring

(e.g. one

3-methyl-1-phenyl-5-pyrazolone-,
1-phenyl-5-pyrazolone-,
l- (2-Benzthiazolyl) -3-methyl-5-pyrazolone ring),

an isoxazolone ring

(e.g. a 3-phenyl-5-isoxazolone or
3-methyl-5-isoxazolone ring),
an oxynediol ring
(e.g. one

1 - alkyl-2,3-dihydro-2-oxynediol ring), a 2,4,6-triketohexahydropyrimidine ring

(e.g. a barbituric acid or 2-thiobarbituric acid ring including the Derivatives thereof which are substituted in the 1-position by an alkyl group, e.g. B. a methyl, Ethyl, 1-n-propyl or 1-n-heptyl group or in the 1 and 3 positions by an alkyl, 0-MethoxyäthyJ- or . Aryl group, e.g. B. a phenyl group,

in particular a p-chlorophenyl or p-ethoxycarbonyl group, or only in the .. '■' · '. .,, '! Position by a phenyl, p-chlorophenyl or p-ethoxy carbonylphenyl group can be substituted),

a rhodanine ring,
ie a 2-thio-2,4-thiazolidinedione ring (e.g. the rhodanine ring itself,
an aliphatic substituted one
Rhodanine ring _; ,.

,. '(such as a'3-Ethylrhodariin-Öder

3- allyl rhodariin ring),
a 2-imidazo [l, 2-a] pyridone ring, an SJ-

azolo [3,2-a] pyrimidine ring (for example a 5,7-dioxo-3-phenyl-6,7-dihydro-5H-thiazolo [3,2-a] pyrimidine ring) ^;

of a 2-thio-2,4-oxazoiidinedione ring ^ ' i.e. a 2-thio-2,4-oxazoldione ring (e.g. a 2-ethyl-2-thio-2,4-oxazolidine

dione ^ring):

of a thianaphthenone ring ^: "- ■: ■ '' ■ '

(e.g. a 3-thianaphthenone ring),;

of a 2-thio-2,5-thiazolidinedione ring ^,! ie a 2-thio-2,5-thiazolidioriringes (e.g. a 3-ethyl-2-thio-2,5-thiazolidinedione ring), '

a 2,4'thiazolidinedione ring (e.g. a 2,4 ^: thiazölidinedione, ■ '·' ■ '3-a-naphthyl-2,4-thiazolidinedione ring),

a 2-imino-4-thiazolidone ring, ie a pseudothiohydantoin ring ■ (e.g. a 2-imino-4-thiazolidone, 3-ethyl-2-imino-4-thiazolidone, ^r

3-phenyl-2-imino-4-thiazolidone- or 3- <x-naphthyl-2-imino-4-thiazolidone ring), .

a 4-thiazolone ring
(e.g. a 2-ethylmercapto-4-thiazolone, 2-alkylphenylamino-4-thiazolone or 2-diphenylamino-4-thiazolone ring),

a 2-imino-4-oxazolidone ring, d. H. a pseudohydantoin ring,

a 2,4-imidazolidinedione ring (e.g. a 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, 3-phenyl-2,4-imidazolidinedione-, 3-a-naphthyl-2,4-imidazolidinedione-,

l-ethyl-3-phenyl-2,4-imidazolidinedione-,

l-ethyl-3-a-naphthyl-2,4-imidazolidine-

dion or

1, S-diphenyl ^ / t-imidazolidinedione ring), a 2-thio-2,4-imidazolidinedione ring

d. H. a 2-thiohydantione ring

(e.g. a 2-thio-2,4-imidazolidinedione,

3-ethyl-2-thio-2,4-imidazoIidindione-,

S-phenyl ^ -thio ^ -imidazolidinedione-,

3-a-naphthyl-2-thio-

2,4-imidazolidinedione,

1, S-diethyl ^ -thio ^ -imidazolidinedione-,

1-ethyl-3-phenyl-2-thio-

2,4-imidazolidinedione,

1 -ethyl-S-a-naphthyl ^ -thio-

2,4-imidazolidinedione or

1,3-Diphenyl-2-thio-2,4-iiriidazolidin-

dionringes) or
a 5-imidazolone ring

(e.g. one

ä-n-Propylmercapto-S-imidazolonringes) required atoms. ■ · ■■■ ·· ■,.,.

The oxonol methine dyes used in accordance with the invention meet the high requirements imposed on Antihalation or filter dyes are provided for silver halide photographic materials; d. H., they do not cause desensitization or fogging of the light-sensitive silver halide emulsion, are coated with a photographic colloid such as B. gelatin, well tolerated (miscible), can be easily

and in situ in non-diffusible form a photographic one Incorporate recording material, they have a high tinting power and are quickly complete and irreversibly decolorized, without the colored degradation products in alkaline or acidic reducing products Media such as an alkaline photographic developing bath or an acidic one Fixer containing sodium hydrogen sulfite.

Compared to the previously used oxonol methine dyes, they also have the advantage that they are acidic are so that it is not necessary to introduce acidic groups in the dye molecule to their solubility in Increase layers of gelatin, as is the case with pyrazolone oxonol dyes and many others Oxonol dyes is the case (cf. z. B. the abovementioned dye B of DE-AS 10 75 944). aside from that the oxonol methine dyes used according to the invention, especially the symmetrical ones Dyes, produced in a very simple way in a one-step process. For the synthesis of the The pyrazolone oxonol dyes used up to now, on the other hand, must first be produced by the pyrazolone core, then have to be introduced into the solubilizing groups, so that for its production a multi-step process must be used.

A direct comparison between the dye 3-methyl-4- [3- (3-methyl-5-oxy-4-isoxazolyl) -2-propenylidene] -5-isoxazolone (hereinafter referred to as "dye A") and the dye used according to the invention Dye B known from DE-AS 10 75 944 has shown that dye A has a molecular extinction coefficient ε of 9.17 10 ⁴ , while dye B has a molecular extinction coefficient ε of 7.49 χ 10 ⁴ , which means that the dye

N
R ¹ -Ο

15th

20th

25th

30th

A has about 22% higher coloring power than dye B. Since the molecular weight of the Dye B is significantly higher than that of Dye A, the difference is with respect to the Tinting power even greater when comparing the dyes on a weight basis. From this it follows found that in connection with the dye A much thinner layers than with the dye B are produced which is of great importance in particular in the case of multilayer photographic materials is.

If the results are compared with one another, which were obtained when 50 mg of dye A and 135 mg of dye B per m ^{2 were incorporated} into a cast gelatin layer, the result is that a smaller amount of dye A has a higher coloring capacity receives. The following values were obtained for the densities read off at absorption maxima:

D = 1.17 at 505 nm for the gelatin layer with the

Dye A and
D = 0.98 at 530 nm for the gelatin layer with the dye B.

In addition, the dye A absorbs more strongly in the inherent sensitivity range of the silver halide (<500 nm) than the dye B.

The oxonol methine dyes used according to the invention can be prepared by various methods which are described in more detail below.

According to a first method, symmetrical and asymmetrical trimethine dyes can be produced according to this Manufacture of the invention by condensation of an isoxazolone compound of the general formula III:

C = O

-C = C-CH ₃ CH ₃ (III)

in which R ^{1 has} the same meaning as above, with a compound of the general formula IV:

Z ¹ -L '= (IV)

in the

L ¹ , P and Q have the same meaning as above and
Z ^{1 is} an optionally substituted amino group, e.g. B. an anilino or acetanilido group, a hydroxyl group, an R ² O or R ² S group, in which R ^{2 is} an alkyl group, e.g. B. a methyl or aralkyl group, e.g. B. a benzyl group.

The condensation is preferably carried out with the supply of heat in the presence of a basic condensing agent, e.g. B. pyridine or triethylamine, carried out, and when Z ^{1 is} an optionally substituted amino group, in the presence of an acid anhydride, for. B. acetic anhydride.

The compound of the general formula III can according to B. Schiff, Ber. 30 (1897), 1340, are made, by mixing acetone with the oxime of a] 3-keto acid ester can condense according to the general formula V:

R ¹ —C — CH ₂ —C OR ³

Il

NOH (V)

in the

R ^{1 has} the same meaning as described above and R ^{3 is} an alkyl group, e.g. B. a methyl group, an aralkyl group, e.g. B. a benzyl group, an aryl group, e.g. B. denotes a phenyl group or a furyl group.

The trimethine dyes to be used according to the invention can also be obtained by a second method as illustrated by the following reaction scheme:

R ¹

C = O CH ₃
-C = C

CH ₃

OR ⁵

+ R ⁴ -C OR ⁵ OR ⁵

basic condensing agent

N
Rc

/ \ C = O ⁰ CH ₃ O = CN

Il I I Il

/ - * / ^ u z " ¹ si (~ * ρ

in the

R ¹ and M® have the same meaning as described above,

R ^{4 is} a hydrogen atom, an alkyl group, for example a

Methyl or ethyl group or an aralkyl group,

z. B. a benzyl group, and

R ^{5 is} an alkyl group, preferably a methyl or

Ethyl group, or an aralkyl group, e.g. B. a benzyl group,

mean.

In the above reaction scheme, the isopropylidene-substituted isoxazolone compound can be represented by the following Connection to be replaced:

/ \
NC = O

Il I

R ¹ -CC = C-CH ₂ -C-OC ₂ H ₅

20th

25 monomethine dyes for use according to the present invention can be prepared by condensation of a compound of the general formula IV with the oxime of a /? - keto acid ester or jS-keto acid amide, which can be represented by the following general formula VII:

Rl /

(VII)

30th

in the

CH,

40

which is based on B. Schiff, Ber. 30 (1897), 1343

According to a third method, can be measured to be used erfindungsge- -v trimethine by con- densation J ■ a compound of the following general formula VI

45

CH ₃
HC = CH-C = OM

Ο ^Θ

(VI)

in the M® preferably a cation of an alkali metal, z. B. sodium, means with the oxime a / 9-keto acid according to the general formula V produce. This condensation is also preferred in the Presence of a basic condensing agent, e.g. B. pyridine performed.

R ^{1 has} the same meaning as described above and R ^{6 is} an alkoxy, preferably a methoxy or ethoxy group, an aralkoxy group, e.g. B. a benzyloxy group, an aryloxy group, e.g. B. a phenyloxy group, a furyloxy group or an optionally substituted amino group, e.g. B. an aromatically substituted amino group, e.g. B. an anilino group means.

In the reaction of this type, the condensation of the oxime occurs at the same time as the isoxazolone ring closure before, so that the dye is formed in one step, starting from the oxime.

The oxime can be prepared by using a j3-ketoester or /? - keto acid amide according to the general Formula VII with a hydroxylamine salt, e.g. B. the hydrochloride, in the presence of a base, e.g. B. Pyridine, piperidine, triethylamine or ammonia, and preferably also in the presence of one Diluent, e.g. B. water, methanol, ethanol, diethyl ether, methylene chloride, chloroform, carbon tetrachloride or dioxane.

Symmetrical methine dyes to be used according to the invention, which have proven to be very suitable can be represented by the following general formula:

O

N CO ⁰ O = CN

Jl ¹ -CC-L ⁴ = (L ⁵ -L ⁶ =) "C CR ¹ .

in which:

030111/1

R ^{1 has} the same meaning as described above, L ⁴ , L ⁵ and L ⁶ each represent an unsubstituted methine group, η 0 or 1 and

M ^{0 is} a cation, e.g. B. a proton, a metal cation or an onium cation of the inorganic or organic type, e.g. B. an ammonium or pyridinium cation.

In the preparation of the symmetrical methine dyes to be used according to the invention, this is allowed Oxime of a 0-keto acid ester or / MCeto acid amide react with a compound capable of converting a methine group or a polymethine chain into the Introduce molecule of methine dyes.

Examples of such compounds correspond to the following general formulas VIII, IX and X:

R ⁷ O

R ⁸ OR ⁷

I /

CH-CH-CH

R ⁷ O OR ⁷

Y ¹ X ¹ -L ⁴ (= L ⁵ -L ⁶ L

(VIII)

(IX)

IO

15th

has the same meaning as described above, a group of the formulas

R ⁹

N =

or

χ2 ^Θ ζ ³ ®N =

20th

25th

30th

35

X ¹ -L ⁴ (= L ⁵ -L ⁶ ) "= A

(X) in which R ⁹ , R ″>, Z ³ , L ⁴ , L ⁵ and L ⁶ each have the same meaning as described above and Χ ^{3Θ denotes} an anion and denotes 0 or 1.

In particular, for the introduction of a monomethine group, an orthoester, ζ. B. methyl orthoformate or ethyl orthoformate, an orthothioester, an amide, thioamide, amide acetal, acyloxy acetal, Amide dichloride or amidine, an iminoether or iminothioether, and for the introduction of a trimethine chain use an alkoxyacrolein acetal, anilinacroleinanil, or malonaldehyde diacetal.

In the reaction of this type, condensation of the oxime with the one methine group or proceeds Methine chain introducing compound at the same time with the isoxazoline ring closure, so that the dye in one step if one starts from the oxime.

Preferably, the condensation reaction with the oxime of a compound is of the following general Formula XI introduced:

40

45

in which mean:

R ^{7 is} an alkyl group,

R ^{8 is} a hydrogen atom or an alkyl group,

Χ ', Y': ■■ ·; ■■

and Z ² each represents a halogen atom, one

N group

in which Z ³ denotes the atoms required to complete a heterocyclic ring, a hydroxyl, R ⁷ O, R ⁷ COO, R ⁷ S or R ⁷ Se group, in which R ^{7 has} the same meaning as described above , or one

R ⁹

N - group

R ^:

55

60

in which R ¹ and R ¹⁰ (identical or different) each denotes a hydrogen atom or an alkyl, aryl or an acyl group, an oxygen, sulfur or selenium atom or an R ⁹ —N group, in which R ⁹ denotes the R ¹ -C-CH ₂ -CR ¹¹ OO

Indian: ■ '■■■ ... ■ ... ■■■ '■. ■■ · .. , - ■ : ■■ · ·.

R ^{1 has} the same meaning as described above and R ^{11 is} an alkoxy group, preferably a methoxy or ethoxy group, an aralkoxy, aryloxy, furyloxy or optionally substituted amino group, e.g. B. means an aromatically substituted amino group, for example an anilino group.

This oxime is made by reacting this compound with a hydroxylamine salt, e.g. B. the hydrochloride, in the presence of a base, e.g. B. pyridine, piperidine, triethylamine or ammonia, and preferably also in the presence of a diluent, e.g. water, methanol, ethanol, diethyl ether, Methylene chloride, chloroform, carbon tetrachloride or dioxane.

Although the 3-methyl-4 - [(3-methyl-5-oxy-4-isoxazolyl) -methylene] -5-isoxazolone dye is preferably prepared by the method of the present invention, one can also use the method of Papini, Gazz. Chim. shark. 81 (1951), 230-235 apply.

The following examples explain the manufacturing possibilities of those to be used according to the invention Oxonolmethine dyes, without, however, seeking protection for these manufacturing possibilities.

Manufacturing 1
3-methyl-4- [1-methyl-3- (3-methyl-5-oxy-4-isoxazolyl) -2-propenylidene] -5-isoxazolone

O

N C = O Ο — C N.

H ₃ CC -C = C-CH = CH-C C-CH ₃

CH ₃

Method l (a)

To a solution of 2.8 g (0.015 mol) of 3-methyl-4-anilinomethylene-5-isoxazolone in a mixture of 15 ml of pyridine and 2.1 ml (0.015 mol) of triethylamine are added 2.1 g (0.05 mol) 3-methyl-4-isopropylidene-5-isoxazolone, manufactured according to B. Schiff (Ber. 30, 1340), and 1.5 ml Acetic anhydride. The reaction mixture is heated on a water bath for half an hour. After Cooling, the solution is acidified with 2N hydrochloric acid. The one precipitated in its acidic form Oxonol dye is suction filtered and washed with water, isopropanol and ether. Then he gets out a mixture of dimethylformamide and water recrystallized. Melting point: 250 ° C (decomposition). Yield: 30%. Absorption maximum in methanol: 515 nm.

Method l (b)

A solution of 8.9 g (0.064 mol) of 3-methyl-4-isopropylidene-5-isoxazolone in a mixture of 8 ml of pyridine and 6.4 ml (0.042 mol) of ethyl orthofromate is 3 Heated on a water bath for hours. While cooling the mixture in ice, add 8 ml of ether and leave crystallize the dye. Yield in the form of the pyridinium salt: 0.7 g (7%). Melting point after the Recrystallization from a mixture of pyridine and ether: 228 ° C (decomposition). Absorption maximum in Methanol: 515 nm.

Method l (c)

20th

25th

30 Manufacturing 2

3-methyl-4 - [(2-thio-3-ethyl-4-oxy-5-thiazolyl) -methylene] -5-isoxazolone

H, C-CC = O
-C = CH-C '

Il

HO-C-

C = S

-NC ₂ H ₅

35

40

45

50 To a solution of 2.86 g (0.022 mol) of ethyl acetoacetate in 25 ml of ethanol are added 1.53 g (0.022 mol) of hydroxylamine chlorohydrate and 2.22 g (0.022 mol) of triethylamine. The mixture is stirred for half an hour at room temperature and a solution of ethyl oximinobutyrate is obtained.

6.12 g (0.02 mol) of S-ethyl-S-acetanilidomethylene rhodamine and 4.04 g (0.04 mol) of triethylamine are added to this solution. The reaction mixture is heated I ¹ Ii hours on a water bath under reflux cooling. After cooling, the dye is precipitated by adding 12 ml of 2 η-hydrochloric acid, suction filtered, washed successively with water, isopropanol and ether, and recrystallized from 40 ml of ethylene glycol monomethyl ether. Yield: 2.7 g (50%). Melting point: 230-234 ° C. Absorption maximum: 460 nm. Ε = 4.5 χ 10 ".;\;

Manufacturing 3

3-methyl-4- [1- (1-phenyl-3-methyl-5-oxy-4-pyrazolyl) ethylidene] -5-isoxazolone

First 13.5 ml (0.1 mol) of ethyl acetoacetate are added to a solution of 8.4 g (0.1 mol) of sodium hydrogen carbonate in 50 ml of water and then 7 g (0.1 mol) of hydroxylamine chlorohydrate are added in portions with stirring! The reaction mixture is left to stand for half an hour and the oxime formed is extracted three times with ether. After drying the ether extracts over anhydrous calcium chloride, 5.4 g (0.05 mol) of formylacetone sodium salt and 60 ml of pyridine are added and the mixture is heated on a water bath for 2 hours in order to slowly evaporate the ether. The dye formed is separated off and purified as in method l (a). Melting point: 250-26O ⁰ C (decomposition). Yield: 11%. Absorption maximum in methanol: 513 nm.

C-CH,

To a solution of 4.29 g (0.033 mol) of ethyl acetoacetate 2.3 g are added to 25 ml of pyridine

(0.033MoI) hydroxylamine chlorohydrate and "3.33 g (0.033 mole) triethyfamine. The mixture is stirred for half an hour at room temperature and a Solution of ethyl oximinobutyric acid. 7.32 g (ff.03 mol) are added to this solution 1-phenyl-3-methyl-4- (a-ethoxyethylidene) -5-pyrazolone and 3.03 g (0.03 mol) of triethylamine. The reaction mixture is heated for 1/2 hour on a water bath. A colorless product crystallizes out on cooling is sucked off; The dye is precipitated through

10 Addition of an excess of dilute hydrochloric acid. Then the dye is filtered off, washed with water and recrystallized from ethanol. Yield: 0.6 g (7%). Melting point: 232-234 ° C. Absorption maximum: 440 nm.e = 2, l χ 10 ⁴ .

Manufacturing 4

3-methyl-4 - [(3-methyl-5-oxy-4-isoxazolyl) methylene] -5-isoxazolone

3 L, -

C = O © O-C

can be prepared by the following two methods 4 (a) and 4 (b).

Method 4 (a)

23.4 g (0.157 mol) of the sodium salt of 3-methyl-4-formyl-5-isoxazolone, prepared according to P. Papini, Gazz. Chim. shark. 80 (1950), 846, are dissolved in 130 ml of water. This solution is cooled in an ice bath and 15.7 ml of strong hydrochloric acid are added. The precipitated 3-methyl-4-formyl-5-isoxazolone is suction filtered and washed with water. The precipitate is then dissolved in 30 ml of strong hydrochloric acid and the resulting solution is stored at room temperature for 3 days. During this period 3-methyl-4 - [(3-methyl-5-oxy-4-isoxazolyl) -methylene] -5-isoxazolone precipitates. The dye is filtered off with suction, washed with water and recrystallized from acetic acid. Yield: 21%. Melting point: 148 ⁰ C. absorption maximum in methanol. 414 nm ε = 2.95 χ ΙΟ. ⁴

Method 4 (b)

First 13.5 ml are added to a solution of 8.4 g (0.1 mol) of sodium hydrogen carbonate in 50 ml of water (0.1 mol) ethyl acetoacetate and then 7 g (0.1 mol) of hydroxylamine chlorohydrate in portions with stirring to. The reaction mixture is left to stand for half an hour and the oxime formed is extracted three times with ether. After drying the ether extracts over anhydrous calcium chloride, one gives

15 ml (0.1 mol) of ethyl orthoformate and 8 ml (0.1 mol) of pyridine and heated the mixture for 2 hours on a Water bath to slowly evaporate the ether. The dye crystallizes out as a pyridinium salt, the separated and washed with ether. Yield:

70%. Melting point: 128-13O ⁰ C. absorption maximum in methanol. 415 nm ε = 3.10 χ 10. ⁴

The oxonol free dye becomes acidic by dissolving the pyridinium salt in water and then dissolving it Cases achieved with hydrochloric acid.

Yield: 73%. Melting point: 148 ° C. Maximum absorption in methanol: 414 nm. Ε = 3.10 χ ΙΟ ⁴ .

Manufacturing 5

3-methyl-4- [3- (3-methyl-5-oxy-4-isoxazolyl) -2-propenylidene] -5-isoxazolone - _: ....

■ θ,

N C = O "O-C

H, C-C C = CH-CH = CH-C-

Il -

-C-CH ₃

H®

can be made by the following two methods:

Method 5 (a)

The oxime is prepared as described in Method 4 (b). Add 8 ml to the ether extracts (0.1 mole) pyridine and 8.2 g (0.05 mole) malondialdehyde tetramethyl acetal. The ether is evaporated and the residue is heated on a water bath for 2 hours. Of the Oxonol dye partially crystallizes out as a pyridine salt. Then the reaction mixture is treated with hydrochloric acid acidified, sucked off the oxonol dye in its acidic form and washed with water. Yield: 3.6 g (30%). Melting point: 260 ° C.

Method 5 (b)

To a solution of 13.5 ml (0.1 mol) of ethyl acetoacetate in 20 ml of methanol and 8 ml (0.1 mol) Pyridine, 7 g (0.1 mol) of hydroxylamine chlorohydrate are added, which gradually dissolves with slow heating so dissolves. Another 8 ml of pyridine and 8.2 g (0.05 mol) of malondialdehyde tetramethyl acetal are added to this solution and heated the mixture on a water bath for 2 hours.

This mixture is then poured into 100 ml of 1N hydrochloric acid. The dye precipitate formed is filtered off with suction and washed with water. Yield: 39 g (33%). Melting point: 260 ⁰ C. absorption maximum in methanol: 503 Hm-E = S ₁ ISxIO. ⁴
The dyes represented by the above general formula can be incorporated into a photographic material by known techniques. They can be incorporated both light-sensitive silver halide layers and non-light-sensitive colloid layers, which can be above, below or between the light-sensitive layers. When used as filter dyes in a light-sensitive silver halide emulsion layer, these dyes reduce inherent sensitivity and /

or the spectral sensitivity of the silver halide is little or no.

It is possible to use one or more filter layers according to the present invention in a color photographic To use multilayer material with three light-sensitive layers and to use a carrier, which is provided with an antihalation layer that is in contact with the latter silver halide emulsion layer stands. The structure of a color photographic multilayer material can look like this: an ordinary blue-sensitive silver halide emulsion layer, a yellow filter layer, a green-sensitized one Silver halide emulsion layer, a red filter layer, a red sensitized silver halide emulsion layer, an antihalation layer that absorbs at least red light, an adhesive layer, and a support.

If the dyes must be in a non-diffusible form, the methine dyes are the general formulas used in their silver salt form. These salts can be formed by Silver nitrate can react with the methine dyes in acidic form or soluble salt form.

The following examples illustrate the invention.

example 1

A pink layer with a color density of 1.05 at A _max = 521 nm is obtained if a carrier made of cellulose triacetate with a mixture of gelatin and a dye prepared according to preparation 1 - method l (b) is applied to an order of 50 mg of dye per m ² coated.

Example 2

A yellow layer with a color density is obtained

of 0.75 at X _max 466 nm when a support is coated with a mixture of gelatin and the dye prepared according to preparation 2 to give an application of 190 mg of dye per m ^2.

Example 3

A yellow layer with a color density is obtained

of 0.5 at A _ma * = 443 nm, when a carrier made of cellulose triacetate is coated with a mixture of gelatin and the dye prepared according to preparation 3 to give an amount of 200 mg of dye per m ^2.

Example 4

A yellow layer with a color density of 1.15 at A _max = 415 nm is obtained if a support with a mixture of gelatin and the dye prepared according to method 4 (b) of preparation 1 is applied to an application of 135 mg of dye per m ² coated.

Example 5

A pink layer with a color density of 1.0 at Amax = 508 nm is obtained if a support with a mixture of gelatin and the dye prepared according to method 5 (b) of preparation 2 is applied to an application of 50 mg dye per m ² coated.

030 111/1

Claims (1)

Patent claims: 1. Photosensitive photographic recording material, which in at least one of its Colloid layer (s) contains an oxonol methine dye, characterized in that the oxonol methine dye is a compound of the general Formula I is present: